TWI845643B - Film adhesive and semiconductor processing sheet - Google Patents

Abstract

The present invention is a film adhesive which is thermosetting and satisfies the following requirements 1) and 2) after being stored at 40°C for 7 days and before being thermosetted. 1) The storage elastic modulus G' of the film adhesive at 80°C is 3×10 ⁴ Pa or less. 2) On the copper wiring side of a glass substrate having a copper wiring with a line/space (L/S) of 100μm/100μm and a thickness of 10μm, in an area of 1.1mm×5mm in the central part of a portion where the film adhesive of 10mm×10mm×20μm is pressed at 80°C with a load of 1.96N for 1 second, the air residual rate in 100% of the spacing portion is 20% or less.

Description

Film adhesive and semiconductor processing sheet

The present invention relates to a film adhesive and a semiconductor processing sheet. This application claims priority based on Japanese Patent Application No. 2019-054995 filed in Japan on March 22, 2019, and the contents of the application are cited herein.

The semiconductor chip is usually bonded to the circuit forming surface of the substrate by means of a film adhesive attached to the inner surface of the semiconductor chip. Then, the obtained product is used to make a semiconductor package, and the semiconductor package is used to finally manufacture the target semiconductor device.

A semiconductor chip having a film adhesive on the back side (a semiconductor chip with a film adhesive) is produced, for example, by using a semiconductor wafer having a film adhesive on the back side and simultaneously performing the division of the semiconductor wafer into semiconductor chips and the cutting of the film adhesive. As such a method, for example, a method of using a dicing blade to divide a semiconductor wafer and simultaneously cutting the film adhesive is known (see Patent Document 1). In this case, the film adhesive before cutting is sometimes also layered on a dicing blade for fixing the semiconductor wafer during dicing and formed into a single body to be used as a dicing adhesive. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2012-222002.

[The problem that the invention wants to solve]

In the above method, when the properties of the film adhesive are insufficient, for example, when a semiconductor package is manufactured using a semiconductor chip with a film adhesive, peeling may occur between the semiconductor chip and the substrate or between the semiconductor chips in the heated semiconductor package, thereby reducing the reliability of the semiconductor package.

The purpose of the present invention is to provide a film adhesive and a semiconductor processing sheet having the film adhesive, wherein the film adhesive has high stability when a chip with the film adhesive is bonded to a circuit forming surface of a substrate and then a semiconductor package is manufactured, and a semiconductor package with high reliability can be manufactured. [Means for solving the problem]

That is, the present invention has the following aspects. (1) A film adhesive is thermosetting and satisfies the following requirements 1) and 2) before being thermoset after storage at 40°C for 7 days and before being thermoset. 1) The storage elastic modulus G' of the film adhesive at 80°C is 3×10 ⁴ Pa or less. 2) On the copper wiring side of a glass substrate having copper wiring with a line/space (L/S) ratio of 100μm/100μm and a thickness of 10μm, in an area of 1.1mm×5mm in the central part of a portion of 10mm×10mm×20μm where the aforementioned film adhesive is pressed at 80°C for 1 second under a load of 1.96N, the air retention rate in 100% by area of the aforementioned spacing portion is 20% by area or less. (2) The film adhesive as described in (1) above, wherein the thickness of the film adhesive is 5μm to 50μm. (3) A semiconductor processing sheet having a support sheet, wherein the film adhesive as described in (1) or (2) above is provided on one surface of the support sheet. (4) A semiconductor processing sheet as described in (3) above, wherein the support sheet comprises a substrate and an adhesive layer disposed on one surface of the substrate; the adhesive layer is disposed between the substrate and the film-like adhesive. [Effect of the invention]

According to the present invention, a film adhesive and a semiconductor processing sheet having the film adhesive are provided. The film adhesive has high stability when a chip with the film adhesive is bonded to a circuit forming surface of a substrate and then a semiconductor package is manufactured, so that a semiconductor package with high reliability can be manufactured.

◇Film-like adhesive The film-like adhesive of one embodiment of the present invention is thermosetting and satisfies the following requirements 1) and 2) before being thermosetted after being stored at 40°C for 7 days and after being stored at 40°C for 7 days. 1) The storage elastic modulus G' of the film-like adhesive at 80°C is 3×10 ⁴ Pa or less. 2) For the copper wiring side of a glass substrate having copper wiring with a line/space (L/S) of 100μm/100μm and a thickness of 10μm, in an area of 1.1mm×5mm in the central part of a portion where a 10mm×10mm×20μm film-like adhesive is pressed at 80°C with a load of 1.96N for 1 second, the air retention rate in 100% by area of the spacing portion is 20% by area or less.

In the film adhesive of this embodiment, by satisfying the above-mentioned requirements 1) and 2), when a chip with the film adhesive is bonded to the circuit forming surface of a substrate and then a semiconductor package is manufactured, it is not easy for the semiconductor chip to peel off from the substrate or from each other, so that a semiconductor package with high reliability can be manufactured.

Regarding the relationship between the above requirements 1) and 2), it is considered that if the storage modulus G' in the above requirement 1) is 3×10 ⁴ Pa or less, the gap portion in the above requirement 2) is easily filled with the film adhesive, and the air residual rate is reduced.

In addition, the film adhesive of this embodiment satisfies the above requirements 1) and 2 both when stored at 40°C for 7 days before thermal curing and when stored at 40°C for 7 days before thermal curing. Static storage at 40°C for 7 days is an accelerated treatment equivalent to static storage at room temperature (about 25°C) for 3 months. Therefore, the film adhesive of this embodiment has high storage stability even after long-term storage and can demonstrate the above reliability.

In order to further improve the reliability, the storage elastic modulus G' of the film adhesive of the present embodiment at 80°C is 3×10 ⁴ Pa or less, preferably 9×10 ³ Pa or less, more preferably 7×10 ³ Pa or less, and further preferably 5×10 ³ Pa or less. The temperature of 80°C is the heating temperature of the bonding step using the film adhesive of the present embodiment.

The lower limit of the storage elastic modulus G' of the film adhesive of the present embodiment at 80°C is not particularly limited, and may be 1×10 ³ Pa or more, 1.5×10 ³ Pa or more, or 2×10 ³ Pa or more. If the storage elastic modulus G' at 80°C is greater than the above lower limit, the thickness of the film adhesive is stable when a load is applied in the die bonding step, and a semiconductor package with higher reliability can be manufactured.

As an example of the numerical range of the storage elastic modulus G' of the film adhesive of this embodiment at 80°C, it may be 1×10 ³ Pa to 3×10 ⁴ Pa, 1×10 ³ Pa to 9×10 ³ Pa, 1.5×10 ³ Pa to 7×10 ³ Pa, or 2×10 ³ Pa to 5×10 ³ Pa.

As shown in the examples described below, the lower the storage modulus G' of the film adhesive at 80°C, the lower the above-mentioned air retention rate in the gap portion that may be generated when the film adhesive is press-bonded to the circuit formation surface of the substrate.

From the perspective of improving the reliability of the semiconductor package, the lower the value of the air retention rate, the better. The air retention rate in the above requirement 2) of the film adhesive of this embodiment is 20% by area or less, preferably 19% by area or less, and more preferably 18% by area or less. The lower limit of the air retention rate can be 0% by area, and from the perspective of exerting the reliability of the semiconductor package, it can also be 5% by area or more, and can also be 10% by area or more.

The above-mentioned air retention rate is obtained by the acquisition method and conditions described in the embodiment described later. The air retention rate is obtained by applying a load of 1.96N for 1 second at 80°C to the central part of the portion where the film-like adhesive is pressed from the chip side of the film-like adhesive-attached chip, which is a laminate composed of the above-mentioned film-like adhesive of 10mm×10mm×20μm and a quartz glass chip of 10mm×10mm×100μm, on the copper wiring side of the glass substrate having a copper wiring with a line/space (L/S) of 100μm/100μm and a thickness of 10μm. In the area of 1.1 mm × 5 mm, the film adhesive after compression bonding is observed from the upper surface of the wafer, and the ratio of the area of the portion (air residual area) of the film adhesive not in contact with the glass substrate to 100% of the area of the spacer portion can be obtained [when the area value of the air residual area of the spacer portion is A and the area value of the non-air residual area of the spacer portion is B, the air residual rate of the spacer portion (area %) = A/(A+B)×100]. The wafer may be a transparent wafer. The non-air-residue area and the air-residue area that are in contact with the film adhesive have different tones of the film adhesive visible through the chip, so the air-residue area can be easily distinguished by visual inspection. Similarly, the air-residue part can also be distinguished by using an image analyzer to analyze the difference in brightness or color of the acquired image. The air-residue rate can be calculated using the image analyzer.

In this embodiment, the film-like adhesive that is the object of the above requirements 1) and 2) is preferably not stored at a temperature exceeding 25°C since the film-like adhesive is manufactured, and the storage time at a temperature below 25°C is within 1 year. Furthermore, the storage conditions of the film-like adhesive other than the temperature at this time are as follows. That is, the film-like adhesive is preferably stored in an air atmosphere, preferably stored statically, and preferably stored in a dark place. Furthermore, it is more preferable to store it in a manner that satisfies two or more of these conditions, and it is particularly preferable to store it in a manner that satisfies all of the conditions.

In this specification, the surface of a semiconductor chip on which a circuit is formed is referred to as a "circuit forming surface", and the surface opposite to the circuit forming surface is referred to as an "inner surface". Furthermore, a structure having a semiconductor chip and a film-like adhesive disposed on the inner surface of the semiconductor chip is referred to as a "semiconductor chip with film-like adhesive". In addition, in this specification, the surface of a substrate on which a circuit is formed is also referred to as a "circuit forming surface". The semiconductor chip with film-like adhesive having the film-like adhesive of this embodiment can be bonded to the circuit forming surface of the substrate in a good state by the film-like adhesive.

The aforementioned film adhesive may be composed of one layer (single layer) or may be composed of two or more layers. When composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

In addition, in this specification, the case of film adhesives is not limited. The phrase "multiple layers may be the same or different from each other" means "all layers may be the same, all layers may be different, or only some layers may be the same". Furthermore, the phrase "multiple layers may be different from each other" means "at least one of the constituent material and thickness of each layer is different from each other".

The thickness of the aforementioned film adhesive is not particularly limited, preferably 1μm to 50μm, more preferably 3μm to 50μm, further preferably 5μm to 50μm, particularly preferably 5μm to 40μm, and most preferably 5μm to 30μm. When the thickness of the film adhesive is above the aforementioned lower limit, the bonding strength of the film adhesive to the adherend (semiconductor wafer, semiconductor chip) becomes higher. When the thickness of the film adhesive is below the aforementioned upper limit, the film adhesive can be cut more easily in the manufacturing step of the semiconductor chip described later, and the amount of cut pieces from the film adhesive can be further reduced, which is conducive to making the semiconductor device thinner. Here, the so-called "thickness of the film-like adhesive" means the thickness of the film-like adhesive as a whole. For example, the so-called thickness of a film-like adhesive composed of multiple layers means the total thickness of all the layers constituting the film-like adhesive.

The aforementioned film-like adhesive can be formed using an adhesive composition containing the constituent materials of the aforementioned film-like adhesive. For example, the adhesive composition is applied to the surface of the object to be formed of the film-like adhesive, and it is dried as needed, thereby forming a film-like adhesive at the target site. The ratio of the content of the components that do not vaporize at room temperature in the adhesive composition is usually the same as the ratio of the content of the aforementioned components in the film-like adhesive. In addition, in this specification, the so-called "normal temperature" means a temperature that is not particularly cold or particularly hot, that is, a normal temperature, for example, a temperature of 15°C to 25°C, etc.

The adhesive composition may be applied by a known method, for example, the following methods using various coaters may be cited: air knife coater, scraper coater, rod coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, Meyer rod coater, touch coater, etc.

The drying conditions of the adhesive composition are not particularly limited. When the adhesive composition contains a solvent described below, it is preferably dried by heating. The adhesive composition containing the solvent is preferably dried at 70°C to 130°C and for 10 seconds to 5 minutes. The following is a detailed description of the film adhesive and the components contained in the adhesive composition.

[Adhesive composition] As a preferred adhesive composition, a thermosetting adhesive composition can be cited. As an example of a thermosetting adhesive composition, a composition containing a polymer component (a) and a thermosetting component (b) can be cited. Each component is described below.

[Polymer component (a)] Polymer component (a) is a component that can be regarded as a polymerizable compound formed by a polymerization reaction. It is used to impart film-forming properties and flexibility to a film-like adhesive and is a polymer compound used to improve the adhesion (adhesion) to a bonding object such as a semiconductor chip. Polymer component (a) has thermoplastic properties and does not have thermosetting properties. In addition, in this specification, the polymer compound also includes products of condensation reactions.

The polymer component (a) contained in the adhesive composition and the film-like adhesive may be only one kind or two or more kinds. When two or more kinds are used, the combination and ratio of these can be arbitrarily selected.

Examples of the polymer component (a) include acrylic resins, urethane resins, phenoxy resins, silicone resins, saturated polyester resins, and the like, with acrylic resins being preferred.

As the aforementioned acrylic resin in the polymer component (a), known acrylic polymers can be cited. The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin is within this range, it is easy to adjust the bonding force between the film adhesive and the adherend to a preferred range. On the other hand, when the weight average molecular weight of the acrylic resin is above the aforementioned lower limit, the shape stability (time stability during storage) of the film adhesive is improved. In addition, by making the weight average molecular weight of the acrylic resin below the aforementioned upper limit, the film adhesive becomes easy to follow the uneven surface of the adherend, and the generation of gaps between the adherend and the film adhesive can be further suppressed. In addition, in this specification, the so-called "weight average molecular weight" refers to the polystyrene conversion value measured by gel permeation chromatography (GPC) unless otherwise specified.

The glass transition temperature (Tg) of the acrylic resin is preferably -60°C to 70°C, more preferably -30°C to 50°C. When the Tg of the acrylic resin is above the lower limit, the bonding force between the film adhesive and the adherend is suppressed, and the semiconductor chip with the film adhesive is more easily pulled off from the support sheet described later when picking up. When the Tg of the acrylic resin is below the upper limit, the bonding force between the film adhesive and the semiconductor chip is improved.

Examples of the (meth)acrylates constituting the acrylic resin include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, and 1,2-dimethyl (meth)acrylate. ) octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate (palmityl (meth)acrylate), heptadecyl (meth)acrylate, (Meth)acrylate alkyl esters whose alkyl group constituting the alkyl ester is a chain structure with a carbon number of 1 to 18, such as octadecyl (meth)acrylate (stearyl (meth)acrylate); (meth)acrylate cycloalkyl esters such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate; (meth)acrylate aralkyl esters such as benzyl (meth)acrylate; (meth)acrylate cycloalkenyl esters such as dicyclopentenyl (meth)acrylate; (meth)acrylate cycloalkenyloxyalkyl esters such as dicyclopentenyloxyethyl (meth)acrylate; (meth)acrylate imide; (meth)acrylate containing glycidyl group such as (meth)acrylate; (meth)acrylate containing hydroxyl group such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; (meth)acrylate containing substituted amino group such as N-methylaminoethyl (meth)acrylate, etc. Here, the so-called "substituted amino group" means a group having a structure in which one or two hydrogen atoms of an amino group are replaced by a group other than hydrogen atoms.

In addition, in this specification, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid.

The acrylic resin may be, for example, a resin obtained by copolymerizing, in addition to the aforementioned (meth)acrylate, one or more monomers selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-hydroxymethylacrylamide.

The monomers constituting the acrylic resin may be one kind or two or more kinds. When there are two or more kinds, the combination and ratio of these monomers can be arbitrarily selected.

In addition to the above-mentioned hydroxyl groups, acrylic resins may also have functional groups such as vinyl, (meth)acryl, amino, carboxyl, and isocyanate groups that can bond with other compounds. These functional groups represented by hydroxyl groups in acrylic resins can bond with other compounds via the crosslinking agent (f) described below, or can directly bond with other compounds without the crosslinking agent (f). By using the above-mentioned functional groups of acrylic resins to bond with other compounds, the reliability of the package obtained using the film adhesive tends to be improved.

In the acrylic resin, the ratio (content) of the amount of the constituent unit derived from the glycidyl group-containing monomer relative to the total amount of the constituent units constituting the acrylic resin is preferably 25 mass % or less, for example, it can be any one of 15 mass % or less and 10 mass % or less. When the above ratio (content) is below the above upper limit, the storage stability of the film-like adhesive becomes higher. In addition, the above glycidyl group-containing monomer refers to, for example, a monomer having a glycidyl group such as the above glycidyl group-containing (meth)acrylate.

In the acrylic resin, the lower limit of the ratio (content) of the amount of the constituent units derived from the glycidyl group-containing monomer relative to the total amount of the constituent units constituting the acrylic resin is not particularly limited. In the acrylic resin, the above ratio (content) may be 0% by mass or more. For example, if it is 2% by mass or more, the effect of using the glycidyl group-containing monomer can be more significantly obtained.

In the acrylic resin, the ratio (content) of the amount of the constituent units derived from the monomers containing a glycidyl group relative to the total amount of the constituent units constituting the acrylic resin can be appropriately adjusted to be within the range set by arbitrarily combining any of the above-mentioned lower limit values and upper limit values. For example, in one embodiment, the aforementioned ratio is preferably 0 mass % to 25 mass %, for example, it can be any one of 0 mass % to 15 mass % and 0 mass % to 10 mass %. In addition, in one embodiment, the aforementioned ratio is preferably 2 mass % to 25 mass %, for example, it can be any one of 2 mass % to 15 mass % and 2 mass % to 10 mass %. However, these are examples of the aforementioned ratios.

In the present invention, instead of using an acrylic resin, a thermoplastic resin other than an acrylic resin (hereinafter, sometimes simply referred to as a "thermoplastic resin") may be used alone as the polymer component (a), or it may be used in combination with an acrylic resin. By using the aforementioned thermoplastic resin, it may be easier to pull a semiconductor chip with a film-like adhesive from a support sheet described later during pickup, or the film-like adhesive may be easier to follow the uneven surface of the adherend, and the generation of gaps between the adherend and the film-like adhesive may be further suppressed.

The weight average molecular weight of the thermoplastic resin is preferably 1,000 to 100,000, more preferably 3,000 to 80,000.

The glass transition temperature (Tg) of the thermoplastic resin is preferably -30°C to 150°C, more preferably -20°C to 120°C.

Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, and polystyrene.

The adhesive composition and the film-like adhesive may contain only one type of the above-mentioned thermoplastic resin or two or more types. When two or more types are contained, the combination and ratio of these resins may be arbitrarily selected.

In the adhesive composition, regardless of the type of polymer component (a), the ratio of the content of the polymer component (a) to the total content of all components other than the solvent (i.e., the ratio of the content of the polymer component (a) in the film-like adhesive to the total mass of the film-like adhesive) is preferably 5% by mass to 40% by mass, more preferably 6% by mass to 30% by mass, for example, 7% by mass to 20% by mass, etc. When the ratio is above the lower limit, the structure of the film-like adhesive is further stabilized.

In the adhesive composition and the film-like adhesive, the content of the acrylic resin relative to the total content of the polymer component (a) is preferably 25% by mass to 100% by mass, for example, 50% by mass to 100% by mass, 70% by mass to 100% by mass, and 90% by mass to 100% by mass. When the content ratio is greater than the lower limit, the storage stability of the film-like adhesive becomes higher.

[Thermosetting component (b)] Thermosetting component (b) is a component that has thermosetting properties and is used to thermoset the film-like adhesive. Thermosetting component (b) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types. When there are two or more types, the combination and ratio of these components may be arbitrarily selected.

Examples of the thermosetting component (b) include epoxy-based thermosetting resins, polyimide resins, and unsaturated polyester resins. Among these, the thermosetting component (b) is preferably an epoxy-based thermosetting resin.

〇Epoxy-based thermosetting resin The epoxy-based thermosetting resin is composed of an epoxy resin (b1) and a thermosetting agent (b2). The epoxy-based thermosetting resin contained in the adhesive composition and the film-like adhesive may be only one type or two or more types. When there are two or more types, the combination and ratio of these resins may be arbitrarily selected.

[Epoxy resin (b1)] As the epoxy resin (b1), there can be listed known epoxy resins, for example, there can be listed: polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated product, o-cresol novolac epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin and other epoxy compounds having two or more functions.

As the epoxy resin (b1), an epoxy resin having an unsaturated hydrocarbon group may also be used. An epoxy resin having an unsaturated hydrocarbon group has a higher compatibility with the acrylic resin described later than an epoxy resin having no unsaturated hydrocarbon group. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained using the film adhesive is improved.

As an epoxy resin having an unsaturated hydrocarbon group, for example, there can be cited a compound having a structure in which a part of the epoxy groups of a polyfunctional epoxy resin is converted into a group having an unsaturated hydrocarbon group. Such a compound is obtained, for example, by subjecting (meth)acrylic acid or a derivative thereof to an epoxy group by an addition reaction. In addition, in this specification, the so-called "derivative", unless otherwise specified, means a compound having a structure in which one or more groups of the original compound are substituted by a group (substituent) other than the group. Here, the so-called "group" includes not only an atomic group composed of a plurality of atoms bonded together, but also a single atom.

In addition, examples of epoxy resins having unsaturated hydrocarbon groups include compounds in which an aromatic ring constituting the epoxy resin is directly bonded with a group having an unsaturated hydrocarbon group. The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples of the unsaturated hydrocarbon group include ethylene (vinyl), 2-propenyl (allyl), (meth)acryl, (meth)acrylamide, etc., preferably acryl.

The number average molecular weight of the epoxy resin (b1) is not particularly limited, but is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000 in terms of the curability of the film adhesive and the strength and heat resistance of the cured product of the film adhesive. The epoxy equivalent of the epoxy resin (b1) is preferably 100 g/eq to 1,000 g/eq, and more preferably 150 g/eq to 800 g/eq.

The epoxy resin (b1) contained in the adhesive composition and the film-like adhesive may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of these can be arbitrarily selected.

Some commercially available epoxy resins (b1) contain acrylic resin particles (acrylic resin in the form of particles). In this embodiment, by using an epoxy resin (b1) that does not contain acrylic resin particles, for example, even when a component that makes acrylic resin particles easily aggregate by interacting with acrylic resin particles is used as the polymer component (a), the aggregation of such acrylic resin particles can sometimes be suppressed, thereby sometimes improving the storage stability of the film-like adhesive. In order to more specifically achieve this effect, for example, in the adhesive composition, the ratio of the content of acrylic resin microparticles to the total content of all components other than the solvent (i.e., the ratio of the content of acrylic resin microparticles in the film-like adhesive to the total mass of the film-like adhesive) is preferably 0 mass % to 5 mass %, and more preferably 0 mass % to 3 mass %, regardless of the source of the acrylic resin microparticles.

[Thermosetting agent (b2)] Thermosetting agent (b2) functions as a curing agent for epoxy resin (b1). Examples of the thermosetting agent (b2) include: a resin represented by the following general formula (1) (sometimes referred to as "resin (1)" in this specification), and thermosetting agents other than the resin.

[Chemistry 1] (In general formula (1), n is an integer greater than 1)

The thermosetting agent (b2) contained in the adhesive composition and the film-like adhesive may be only one kind or may be two or more kinds. In the case of two or more kinds, the combination and ratio of these can be arbitrarily selected. For example, the thermosetting agent (b2) in the adhesive composition and the film-like adhesive may contain only the resin (1), only a thermosetting agent other than the resin (1), or both the resin (1) and a thermosetting agent other than the resin (1).

・Resin (1) More specifically, the resin (1) is an o-cresol-type phenolic varnish resin. In the general formula (1), n is an integer greater than or equal to 1, for example, it can be any of 2 or greater, 4 or greater, and 6 or greater. There is no particular limitation on the upper limit of n within a range that does not impair the effect of the present invention. For example, the resin (1) having n less than or equal to 10 is easier to manufacture or obtain.

In the general formula (1), the bonding position of the methylene group (—CH ₂ —) linking the o-cresol-diyl groups (—C ₆ H ₄ (—OH)(—CH ₃ )-) to the o-cresol-diyl groups is not particularly limited.

Furthermore, the softening point of the resin (1) is preferably 60°C to 130°C. When the softening point of the resin (1) is 60°C or higher, the force of the film adhesive to bond the adherends to each other, i.e., the so-called bonding force, can be easily exhibited. When the softening point of the resin (1) is 130°C or lower, the die bonding temperature of the film adhesive can be lowered, and the warping of the substrate after die bonding can be highly suppressed.

The resin (1) contained in the adhesive composition and the film-like adhesive may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of these resins can be arbitrarily selected.

・Thermosetting agents other than resin (1) Thermosetting agents other than resin (1) are not particularly limited as long as they do not conform to resin (1). As thermosetting agents other than resin (1), for example, compounds having two or more functional groups that can react with epoxy groups in one molecule can be listed. As the aforementioned functional groups, for example, phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, and groups formed by anhydriding acid groups can be listed.

Among the thermosetting agents other than the resin (1), examples of phenolic curing agents having a phenolic hydroxyl group include polyfunctional phenolic resins, biphenol, novolac-type phenolic resins, dicyclopentadiene-type phenolic resins, and aralkyl-type phenolic resins. Among the thermosetting agents other than the resin (1), examples of amine-type curing agents having an amine group include dicyandiamide (DICY).

Thermosetting agents other than resin (1) may also have unsaturated hydrocarbon groups. Examples of thermosetting agents other than resin (1) having unsaturated hydrocarbon groups include compounds having a structure in which a portion of the hydroxyl groups of a phenol resin are substituted by a group having an unsaturated hydrocarbon group, and compounds having a structure in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring of a phenol resin. The unsaturated hydrocarbon group in the thermosetting agent other than resin (1) is the same as the unsaturated hydrocarbon group in the above-mentioned epoxy resin having an unsaturated hydrocarbon group.

When a phenolic curing agent is used as a thermosetting agent other than the resin (1), the thermosetting agent other than the resin (1) preferably has a high softening point or glass transition temperature in order to easily adjust the adhesive strength of the film adhesive.

In thermosetting agents other than resin (1), the number average molecular weight of resin components such as multifunctional phenol resins, novolac phenol resins, dicyclopentadiene phenol resins, and aralkyl phenol resins is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000. In thermosetting agents other than resin (1), the molecular weight of non-resin components such as diphenol and cyanamide is not particularly limited, and is preferably 60 to 500, for example.

The thermosetting agent other than the resin (1) contained in the adhesive composition and the film-like adhesive may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of these can be arbitrarily selected.

In the adhesive composition and the film-like adhesive, regardless of the type of the thermosetting agent (b2), the content of the thermosetting agent (b2) relative to 100 parts by mass of the epoxy resin (b1) is preferably 0.1 parts by mass to 500 parts by mass, and more preferably 1 parts by mass to 200 parts by mass, for example, any one of 5 parts by mass to 100 parts by mass and 10 parts by mass to 75 parts by mass. By the aforementioned content of the thermosetting agent (b2) being above the aforementioned lower limit, the film-like adhesive becomes easier to cure. By the aforementioned content of the thermosetting agent (b2) being below the aforementioned upper limit, the moisture absorption rate of the film-like adhesive can be reduced, and the reliability of the package obtained using the film-like adhesive is further improved.

In the adhesive composition and the film adhesive, the content of the thermosetting component (b) (for example, the total content of the epoxy resin (b1) and the thermosetting agent (b2)) relative to 100 parts by mass of the polymer component (a) is preferably 100 parts by mass to 900 parts by mass, more preferably 130 parts by mass to 850 parts by mass, and further preferably 160 parts by mass to 800 parts by mass, for example, 400 parts by mass to 800 parts by mass, 500 parts by mass to 800 parts by mass, and 600 parts by mass to 800 parts by mass. By having the aforementioned content of the thermosetting component (b) in such a range, it becomes easier to adjust the bonding force between the film adhesive and the supporting sheet described later.

When the adhesive composition and the film adhesive contain the resin (1), the value of [the amount (mass parts) of the resin (1) in the film adhesive]/[the amount (mass parts) of the epoxy resin (b1) in the film adhesive] (sometimes referred to as "the (1)/(b1) value" in this specification) is preferably greater than 0 and less than 1. When the (1)/(b1) value is less than 1, the film adhesive is highly thermally cured, and as a result, the reliability of the semiconductor package obtained using the film adhesive is improved regardless of whether the semiconductor processing sheet described later is stored or not. On the other hand, since the amount (mass parts) of the resin (1) in the film-like adhesive and in the adhesive composition, and the amount (mass parts) of the epoxy resin (b1) in the film-like adhesive and in the adhesive composition are both positive values, the value of (1)/(b1) is neither 0 (zero) nor a negative value. In addition, the value of [the amount (mass parts) of the resin (1) in the film-like adhesive]/[the amount (mass parts) of the epoxy resin (b1) in the film-like adhesive] is synonymous with the value of [the amount (mass parts) of the resin (1) in the adhesive composition]/[the amount (mass parts) of the epoxy resin (b1) in the adhesive composition].

In order to achieve a higher effect, the (1)/(b1) value may be, for example, any one of 0.1 to 1, 0.2 to 1, 0.3 to 1, and 0.4 to 1; it may also be any one of greater than 0 and less than 0.9, greater than 0 and less than 0.8, greater than 0 and less than 0.7, and greater than 0 and less than 0.6; it may also be any one of 0.1 to 0.9, 0.2 to 0.8, 0.3 to 0.7, and 0.4 to 0.6.

In addition, the (1)/(b1) value is synonymous with, for example, [the ratio of the content of the resin (1) in the film-like adhesive to the total mass of the film-like adhesive (mass %)]/[the ratio of the content of the epoxy resin (b1) in the film-like adhesive to the total mass of the film-like adhesive (mass %)], and is synonymous with [the ratio of the content of the resin (1) in the adhesive composition to the total content of all components other than the solvent (mass %)]/[the ratio of the content of the epoxy resin (b1) in the adhesive composition to the total content of all components other than the solvent (mass %)].

When the resin (1) is used as the thermosetting agent (b2), the storage stability of the film-like adhesive and the adhesive composition tends to be higher than when a thermosetting agent other than the resin (1) is used, which is advantageous for storing these at room temperature.

The film adhesive of this embodiment preferably has thermosetting properties and further has pressure-sensitive adhesive properties. The film adhesive having both thermosetting properties and pressure-sensitive adhesive properties can be attached to various adherends by gently pressing it in an uncured state. In addition, the film adhesive can also be attached to various adherends by heating it to soften it. The film adhesive eventually becomes a highly impact-resistant cured product by curing, and the cured product can maintain sufficient adhesive properties even under severe high temperature and high humidity conditions.

In order to improve the various physical properties of the film adhesive, in addition to the polymer component (a) and the thermosetting component (b), other components that do not conform to these components may be further contained as needed. As other components contained in the film adhesive, for example, hardening accelerator (c), filler (d), coupling agent (e), crosslinking agent (f), energy ray hardening resin (g), photopolymerization initiator (h), general additive (i), etc. can be listed. Among these, as the preferred other components, hardening accelerator (c), filler (d), coupling agent (e) can be listed.

In this specification, the term "energy ray" means an electromagnetic wave or charged particle beam with energy quanta, and examples of such energy ray include ultraviolet rays, radiation, electron beams, etc. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light lamp, or an LED (Light Emitting Diode) lamp as an ultraviolet ray source. Electron beams can irradiate electron beams generated by electron beam accelerators, etc. In this specification, the term "energy ray curability" means the property of curing by irradiation with energy rays, and the term "non-energy ray curability" means the property of not curing even if irradiated with energy rays.

[Hardening accelerator (c)] Hardening accelerator (c) is a component used to adjust the hardening speed of adhesive compositions and film adhesives. Preferred curing accelerators (c) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; imidazoles (imidazoles in which one or more hydrogen atoms are replaced by groups other than hydrogen atoms) such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; organic phosphines (phosphines in which one or more hydrogen atoms are replaced by organic groups) such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenylborates such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate; inclusion compounds having the aforementioned imidazoles as guest compounds, and the like.

The curing accelerator (c) contained in the adhesive composition and the film-like adhesive may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of these accelerators may be arbitrarily selected.

When the curing accelerator (c) is used, the content of the curing accelerator (c) in the adhesive composition and the film-like adhesive is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the content of the thermosetting component (b) (for example, the total content of the epoxy resin (b1) and the thermosetting agent (b2)). When the content of the curing accelerator (c) is equal to or greater than the lower limit, the effect of using the curing accelerator (c) can be more significantly obtained. By making the content of the hardening accelerator (c) below the aforementioned upper limit value, the effect of suppressing the highly polar hardening accelerator (c) from moving toward the bonding interface between the film-like adhesive and the adherend under high temperature and high humidity conditions and segregating in the film-like adhesive is enhanced, thereby further improving the reliability of the package obtained using the film-like adhesive.

[Filling material (d)] By containing a filling material (d), the thermal expansion coefficient of the film-like adhesive can be easily adjusted to be the most suitable thermal expansion coefficient for the object to which the film-like adhesive is attached, thereby further improving the reliability of the package obtained by using the film-like adhesive. In addition, by containing a filling material (d) in the film-like adhesive, the moisture absorption rate of the cured product of the film-like adhesive can be reduced or the heat dissipation can be improved.

The filler (d) may be any of an organic filler and an inorganic filler, preferably an inorganic filler. As preferred inorganic fillers, for example, powders of silica, alumina, talc, calcium carbonate, titanium dioxide, red iron, silicon carbide, boron nitride, etc.; beads obtained by sphericalizing these inorganic fillers; surface-modified products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc. Among these, the inorganic filler is preferably silica, alumina, or surface-modified products of these.

The average particle size of the filler (d) is not particularly limited, and is preferably 10 nm to 5 μm, for example, 10 nm to 800 nm, 10 nm to 600 nm, 20 nm to 300 nm, and 30 nm to 150 nm. When the average particle size of the filler (d) is within this range, the effect of using the filler (d) can be fully obtained, and the storage stability of the film adhesive becomes higher. In addition, in this specification, the so-called "average particle size" means the value of the particle size (D ₅₀ ) at the cumulative value of 50% in the particle size distribution curve obtained by the laser diffraction scattering method unless otherwise specified.

The filler (d) contained in the adhesive composition and the film-like adhesive may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of these fillers can be arbitrarily selected.

When the filler (d) is used, the content of the filler (d) in the adhesive composition is preferably 5 to 30% by mass, more preferably 7 to 25% by mass, and even more preferably 9 to 20% by mass. When the content of the filler (d) is within this range, it becomes easier to adjust the thermal expansion coefficient.

[Coupling agent (e)] By containing a coupling agent (e), the film-like adhesive has improved adhesion and close contact with the adherend. In addition, by containing a coupling agent (e) in the film-like adhesive, the cured product of the film-like adhesive has improved water resistance without impairing heat resistance. The coupling agent (e) has a functional group that can react with an inorganic compound or an organic compound.

The coupling agent (e) is preferably a compound having a functional group that can react with the functional group of the polymer component (a), the thermosetting component (b), etc., and is more preferably a silane coupling agent. As preferred silane coupling agents, for example, 3-glyceryloxypropyl trimethoxysilane, 3-glyceryloxypropyl methyl diethoxysilane, 3-glyceryloxypropyl triethoxysilane, 3-glyceryloxymethyl diethoxysilane, 2-(3,4-epoxyhexyl)ethyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-(2-aminoethylamino)propyl trimethoxysilane, 3-(2- 3-(aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-butylpropyltrimethoxysilane, 3-butylpropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazole silane, oligomer or polymer organic siloxane, etc.

The coupling agent (e) contained in the adhesive composition and the film-like adhesive may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of these can be arbitrarily selected.

When a coupling agent (e) is used, the content of the coupling agent (e) in the adhesive composition and the film-like adhesive is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total content of the polymer component (a) and the thermosetting component (b). When the content of the coupling agent (e) is above the lower limit, the following effects of using the coupling agent (e) can be more significantly obtained: the dispersibility of the filler (d) in the resin is improved, and the adhesion between the film-like adhesive and the adherend is improved. When the content of the coupling agent (e) is below the upper limit, the generation of outgassing can be further suppressed.

[Crosslinking agent (f)] When the above-mentioned acrylic resin having a functional group such as a vinyl group, a (meth)acryl group, an amino group, a hydroxyl group, a carboxyl group, an isocyanate group, etc. that can bond with other compounds is used as the polymer component (a), the adhesive composition and the film-like adhesive may also contain a crosslinking agent (f), which is used to crosslink the above-mentioned functional group with other compounds. By using the crosslinking agent (f) for crosslinking, the initial adhesion and cohesion of the film-like adhesive can be adjusted.

Examples of the crosslinking agent (f) include organic polyisocyanate compounds, organic polyimide compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking agents (crosslinking agents having an aziridine group), and the like.

Examples of the aforementioned organic polyisocyanate compounds include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, and alicyclic polyisocyanate compounds (hereinafter, these compounds are sometimes collectively referred to as "aromatic polyisocyanate compounds, etc."); trimers, isocyanurates, and adducts of the aforementioned aromatic polyisocyanate compounds, etc.; terminal isocyanate urethane prepolymers obtained by reacting the aforementioned aromatic polyisocyanate compounds, etc. with polyol compounds, etc. The aforementioned "adduct" refers to the reaction product of the aforementioned aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, or alicyclic polyisocyanate compounds with a low molecular weight active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trihydroxymethylpropane, or castor oil. Examples of the adduct include the trihydroxymethylpropane xylylene diisocyanate adduct described below. In addition, the so-called "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the terminal of the molecule.

More specifically, the organic polyisocyanate compounds include: 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-phenylenediisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate. diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; a compound prepared by adding any one or two or more of toluene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate to all or part of the hydroxyl groups of a polyol such as trihydroxymethylpropane; lysine diisocyanate, etc.

Examples of the organic polyimide compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trihydroxymethylpropane-tri-β-aziridine propionate, tetrahydroxymethylmethane-tri-β-aziridine propionate, and N,N'-toluene-2,4-bis(1-aziridinecarboxamide) triethylmelamine.

When an organic polyisocyanate compound is used as the crosslinking agent (f), a hydroxyl-containing polymer is preferably used as the polymer component (a). When the crosslinking agent (f) has an isocyanate group and the polymer component (a) has a hydroxyl group, a crosslinking structure can be easily introduced into the film-like adhesive by the reaction between the crosslinking agent (f) and the polymer component (a).

The crosslinking agent (f) contained in the adhesive composition and the film-like adhesive may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of these crosslinking agents can be arbitrarily selected.

The content of the crosslinking agent (f) is preferably 0 to 5 parts by mass, more preferably 0 to 3 parts by mass, further preferably 0 to 1 part by mass, and particularly preferably 0 part by mass relative to 100 parts by mass of the content of the polymer component (a), that is, the adhesive composition and the film-like adhesive do not contain the crosslinking agent (f). When the content of the crosslinking agent (f) is above the lower limit, the effect of using the crosslinking agent (f) can be more significantly obtained. When the content of the crosslinking agent (f) is below the upper limit, the storage stability of the film-like adhesive becomes higher.

[Energy ray curing resin (g)] The adhesive composition and the film-like adhesive may also contain an energy ray curing resin (g). By containing the energy ray curing resin (g), the film-like adhesive can change its properties by irradiating energy rays.

The energy ray-curable resin (g) is obtained by polymerizing (curing) an energy ray-curable compound. As the aforementioned energy ray-curable compound, for example, a compound having at least one polymerizable double bond in the molecule can be cited, preferably an acrylate compound having a (meth)acryloyl group.

Examples of the acrylate compounds include trihydroxymethylpropane tri(meth)acrylate, tetrahydroxymethylmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and the like. (meth)acrylates containing a cyclic aliphatic skeleton; (meth)acrylates containing a cyclic aliphatic skeleton such as dicyclopentanyl di(meth)acrylate; polyalkylene glycol (meth)acrylates such as polyethylene glycol di(meth)acrylate; oligoester (meth)acrylates; (meth)acrylate urethane oligomers; epoxy-modified (meth)acrylates; polyether (meth)acrylates other than the aforementioned polyalkylene glycol (meth)acrylates; itaconic acid oligomers, etc.

The weight average molecular weight of the energy ray-curable resin (g) is preferably 100 to 30,000, more preferably 300 to 10,000.

The energy ray-curable resin (g) contained in the adhesive composition may be only one kind or two or more kinds. When it is two or more kinds, the combination and ratio of these can be arbitrarily selected.

When the energy ray curable resin (g) is used, the content of the energy ray curable resin (g) in the adhesive composition is preferably 1 mass % to 95 mass %, for example, 1 mass % to 50 mass %, 1 mass % to 25 mass %, and 1 mass % to 10 mass %.

[Photopolymerization initiator (h)] When the adhesive composition and the film-like adhesive contain the energy-beam-curable resin (g), a photopolymerization initiator (h) may be contained in order to efficiently perform the polymerization reaction of the energy-beam-curable resin (g).

Examples of the photopolymerization initiator (h) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin benzoic acid methyl ester, and benzoin dimethyl ketal; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, and 2,2-dimethoxy-1,2-diphenylethane-1-one; acyl oxides such as bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, and 2,4,6-trimethylbenzyldiphenylphosphine oxide; Phosphine compounds; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-keto alcohol compounds such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanone compounds such as thiothione; peroxide compounds; diketone compounds such as diacetyl; benzoyl; dibenzoyl; benzophenone; 2,4-diethylthiothione; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone, etc. In addition, as the photopolymerization initiator (h), for example, photosensitizers such as amines can also be listed.

The photopolymerization initiator (h) contained in the adhesive composition and the film-like adhesive may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio of these can be arbitrarily selected.

When a photopolymerization initiator (h) is used, the content of the photopolymerization initiator (h) in the adhesive composition is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass, based on 100 parts by mass of the energy ray-curable resin (g).

[Universal additive (i)] Universal additive (i) can be a known additive and can be selected arbitrarily according to the purpose without particular limitation. Preferred universal additives (i) include, for example, plasticizers, antistatic agents, antioxidants, colorants (dyes, pigments), gettering agents, etc.

The general-purpose additive (i) contained in the adhesive composition and the film-like adhesive may be only one kind or two or more kinds. In the case of two or more kinds, the combination and ratio of these additives can be arbitrarily selected. The content of the general-purpose additive (i) in the adhesive composition and the film-like adhesive is not particularly limited and can be appropriately selected according to the purpose.

[Solvent] The adhesive composition preferably further contains a solvent. The adhesive composition containing a solvent has good operability. The aforementioned solvent is not particularly limited. Examples of preferred aforementioned solvents include: hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having amide bonds) such as dimethylformamide and N-methylpyrrolidone, etc. The solvent contained in the adhesive composition may be only one kind or two or more kinds. In the case of two or more kinds, the combination and ratio of these solvents may be arbitrarily selected.

From the viewpoint of being able to more uniformly mix the components contained in the adhesive composition, the solvent contained in the adhesive composition is preferably methyl ethyl ketone or the like.

As an example of a preferred film adhesive of the present embodiment, the following film adhesive can be cited: it is thermosetting and satisfies the following requirements 1) and 2) before being stored at 40°C for 7 days and before being thermoset, and after being stored at 40°C for 7 days and before being thermoset: 1) the storage elastic modulus G' of the film adhesive at 80°C is 3×10 ⁴ Pa or less; 2) On the copper wiring side of a glass substrate having a copper wiring with a line/space (L/S) ratio of 100 μm/100 μm and a thickness of 10 μm, in an area of 1.1 mm×5 mm in the central portion of a portion where a 10 mm×10 mm×20 μm film adhesive is pressed at 80°C with a load of 1.96 N for 1 second, the air retention rate in 100% by area of the spacing portion is 20% by area or less; The film-like adhesive contains a polymer component (a), an epoxy resin (b1) and a thermosetting agent (b2), wherein the polymer component (a) is an acrylic resin, and the thermosetting agent (b2) is the resin (1). In the film-like adhesive, the content of the polymer component (a) is 6% to 30% by mass relative to the total mass of the film-like adhesive; and in the film-like adhesive, the total content of the epoxy resin (b1) and the thermosetting agent (b2) is 160% to 800% by mass relative to 100% by mass of the polymer component (a).

As another example of a preferred film adhesive of the present embodiment, the following film adhesive can be cited: it is thermosetting and satisfies the following requirements 1) and 2) before being stored at 40°C for 7 days and before being thermoset, and after being stored at 40°C for 7 days and before being thermoset: 1) the storage elastic modulus G' of the film adhesive at 80°C is 3×10 ⁴ Pa or less; 2) On the copper wiring side of a glass substrate having a copper wiring with a line/space (L/S) ratio of 100 μm/100 μm and a thickness of 10 μm, in an area of 1.1 mm×5 mm in the central portion of a portion where a 10 mm×10 mm×20 μm film adhesive is pressed at 80°C with a load of 1.96 N for 1 second, the air retention rate in 100% by area of the spacing portion is 20% by area or less; The aforementioned film-like adhesive contains a polymer component (a), an epoxy resin (b1) and a thermosetting agent (b2), wherein the aforementioned polymer component (a) is an acrylic resin, and the aforementioned thermosetting agent (b2) is the aforementioned resin (1) having a softening point of 60°C to 130°C; in the aforementioned film-like adhesive, the ratio of the content of the aforementioned polymer component (a) to the total mass of the aforementioned film-like adhesive is 6% to 30% by mass; in the aforementioned film-like adhesive, the total content of the aforementioned epoxy resin (b1) and the thermosetting agent (b2) is 160 parts by mass to 800 parts by mass relative to 100 parts by mass of the content of the aforementioned polymer component (a).

As another example of a preferred film adhesive of the present embodiment, the following film adhesive can be cited: it is thermosetting and satisfies the following requirements 1) and 2) before being stored at 40°C for 7 days and before being thermoset, and after being stored at 40°C for 7 days and before being thermoset: 1) the storage elastic modulus G' of the film adhesive at 80°C is 3×10 ⁴ Pa or less; 2) On the copper wiring side of a glass substrate having a copper wiring with a line/space (L/S) ratio of 100 μm/100 μm and a thickness of 10 μm, in an area of 1.1 mm×5 mm in the central portion of a portion where a 10 mm×10 mm×20 μm film adhesive is pressed at 80°C with a load of 1.96 N for 1 second, the air retention rate in 100% by area of the spacing portion is 20% by area or less; The film-like adhesive comprises a polymer component (a), an epoxy resin (b1) and a thermosetting agent (b2), wherein the polymer component (a) is an acrylic resin, and the thermosetting agent (b2) is the resin (1); in the film-like adhesive, the content of the polymer component (a) is 6% to 30% by weight relative to the total weight of the film-like adhesive; In the adhesive, the total content of the epoxy resin (b1) and the thermosetting agent (b2) is 160 to 800 parts by mass relative to 100 parts by mass of the content of the polymer component (a); and the value of [the amount (parts by mass) of the resin (1) in the film-like adhesive]/[the amount (parts by mass) of the epoxy resin (b1) in the film-like adhesive] is greater than 0 and less than 1.

As another example of a preferred film adhesive of the present embodiment, the following film adhesive can be cited: it is thermosetting and satisfies the following requirements 1) and 2) before being stored at 40°C for 7 days and before being thermoset, and after being stored at 40°C for 7 days and before being thermoset: 1) the storage elastic modulus G' of the film adhesive at 80°C is 3×10 ⁴ Pa or less; 2) On the copper wiring side of a glass substrate having a copper wiring with a line/space (L/S) ratio of 100 μm/100 μm and a thickness of 10 μm, in an area of 1.1 mm×5 mm in the central portion of a portion where a 10 mm×10 mm×20 μm film adhesive is pressed at 80°C with a load of 1.96 N for 1 second, the air retention rate in 100% by area of the spacing portion is 20% by area or less; The film-like adhesive comprises a polymer component (a), an epoxy resin (b1) and a thermosetting agent (b2), wherein the polymer component (a) is an acrylic resin, and the thermosetting agent (b2) is the resin (1) having a softening point of 60° C. to 130° C.; in the film-like adhesive, the content of the polymer component (a) is 6% to 30% by weight relative to the total weight of the film-like adhesive. %; in the aforementioned film-like adhesive, the total content of the aforementioned epoxy resin (b1) and the thermosetting agent (b2) is 160 parts by mass to 800 parts by mass relative to 100 parts by mass of the content of the aforementioned polymer component (a); and the value of [the amount of the aforementioned resin (1) in the aforementioned film-like adhesive (parts by mass)]/[the amount of the aforementioned epoxy resin (b1) in the aforementioned film-like adhesive (parts by mass)] is greater than 0 and less than 1.

[Manufacturing method of adhesive composition] The adhesive composition is obtained by mixing the components constituting the adhesive composition. The order of adding the components when mixing is not particularly limited, and two or more components may be added simultaneously. When a solvent is used, the solvent may be mixed with any one of the components other than the solvent and the components may be diluted in advance for use, or the solvent may be mixed with the components without diluting any of the components other than the solvent in advance for use.

There is no particular limitation on the method of mixing the ingredients during preparation, and it can be appropriately selected from the following known methods: a method of mixing by rotating a stirrer or a stirring blade; a method of mixing by using a mixer; a method of mixing by applying ultrasonic waves, etc. Regarding the temperature and time when adding and mixing the ingredients, there is no particular limitation, and it can be appropriately adjusted as long as the ingredients are not degraded. The temperature is preferably 15°C to 30°C.

Fig. 1 is a cross-sectional view of a film adhesive of an embodiment of the present invention. In addition, in order to facilitate understanding of the features of the present invention, for convenience, the following description uses a diagram that sometimes enlarges the portion that is the main part, and is not limited to the size ratio of each constituent element being the same as the actual one.

The film adhesive 13 shown here has a first peeling film 151 on one side (sometimes referred to as "first side" in this specification) 13a of the film adhesive 13, and a second peeling film 152 on the other side (sometimes referred to as "second side" in this specification) 13b opposite to the first side 13a. This film adhesive 13 is suitable for storage in a roll form, for example.

The film-like adhesive 13 can be formed using the above-mentioned adhesive composition.

The first peeling film 151 and the second peeling film 152 may be known peeling films. The first peeling film 151 and the second peeling film 152 may be the same as each other, or may be different from each other because the peeling forces required when peeling the film-like adhesive 13 are different from each other.

In the film adhesive 13 shown in FIG1 , the exposed surface produced by removing one of the first peeling film 151 and the second peeling film 152 becomes the attachment surface of the inner surface of the semiconductor wafer (not shown). In addition, the exposed surface produced by removing the other peeling film remaining after the first peeling film 151 and the second peeling film 152 becomes the attachment surface of the supporting sheet or the dicing sheet described later.

◇Semiconductor processing sheet A semiconductor processing sheet according to one embodiment of the present invention has a support sheet, and the film-like adhesive is provided on one surface of the support sheet. The semiconductor processing sheet is suitable as a wafer bonding sheet, for example.

The semiconductor processing sheet of this embodiment is formed by using the aforementioned film adhesive, so when the semiconductor wafer is divided into semiconductor chips and the film adhesive is cut by dicing at the same time, chip splashing can be suppressed. In addition, the reliability of the semiconductor package formed by using the aforementioned semiconductor processing sheet and introducing the aforementioned film adhesive is high.

[Support sheet] The aforementioned support sheet may be composed of one layer (single layer) or may be composed of two or more layers. When the support sheet is composed of multiple layers, the constituent materials and thicknesses of these multiple layers may be the same or different, and the combination of these multiple layers is not particularly limited as long as it does not impair the effect of the present invention.

As a preferred support sheet, for example, there can be listed: a support sheet consisting only of a substrate; a support sheet having a substrate and an adhesive layer disposed on one surface of the substrate, etc. In the case where the support sheet has the substrate and the adhesive layer, in the semiconductor processing sheet, the adhesive layer is disposed between the substrate and the film adhesive.

The aforementioned support sheet consisting only of a substrate is suitable as a carrier sheet or a dicing sheet. The semiconductor processing sheet having such a support sheet consisting only of a substrate is used by attaching the surface of the film adhesive opposite to the side having the support sheet (i.e., substrate) (sometimes referred to as "first surface" in this specification) to the inner surface of a semiconductor wafer.

On the other hand, the aforementioned support sheet having a base material and an adhesive layer is suitable as a dicing sheet. The semiconductor processing sheet having such a support sheet is also used by attaching the surface (first surface) of the film adhesive opposite to the side having the support sheet to the inner surface of the semiconductor wafer.

The use of the semiconductor processing sheet will be described in detail later. Below, the various layers that make up the support sheet are described.

[Substrate] The aforementioned substrate is in the form of a sheet or a film. As the constituent material of the aforementioned substrate, various resins can be listed. As the aforementioned resin, for example, polyethylene such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE); polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resins; ethylene-vinyl acetate copolymers, ethylene-(meth)acrylic acid copolymers, ethylene-(meth)acrylic acid ester copolymers, and ethylene-norbornene copolymers (copolymers obtained using ethylene as a monomer); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (resins obtained using vinyl chloride as a monomer); polystyrene Ethylene; polycycloolefin; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalate, and all aromatic polyesters having aromatic cyclic groups in all constituent units; copolymers of two or more of the aforementioned polyesters; poly(meth)acrylate; polyurethane; polyacrylic urethane; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; polysulfone; polyether ketone, etc. In addition, as the aforementioned resin, for example, polymer alloys such as a mixture of the aforementioned polyester and a resin other than the aforementioned polyester can also be listed. The polymer alloy of the aforementioned polyester and a resin other than the aforementioned polyester is preferably a relatively small amount of the resin other than the polyester. In addition, examples of the resin include: a crosslinked resin obtained by crosslinking one or more of the resins listed above; and a modified resin such as an ionic polymer using one or more of the resins listed above.

The resin constituting the substrate may be only one type or two or more types. When there are two or more types, the combination and ratio of these types can be arbitrarily selected.

The substrate may be composed of one layer (single layer) or may be composed of two or more layers. When composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

The thickness of the substrate is preferably 50 μm to 300 μm, more preferably 60 μm to 150 μm. When the thickness of the substrate is within this range, the flexibility of the semiconductor processing sheet and the adhesion to the semiconductor wafer or semiconductor chip are further improved. Here, the so-called "thickness of the substrate" means the thickness of the substrate as a whole. For example, the thickness of a substrate composed of multiple layers means the total thickness of all layers constituting the substrate.

The substrate preferably has high thickness accuracy, that is, preferably has thickness deviation suppressed regardless of the location. Among the above-mentioned constituent materials, materials that can be used to form such a substrate with high thickness accuracy include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, etc.

The substrate may contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, softeners (plasticizers), etc. in addition to the main constituent materials such as the aforementioned resin.

The substrate can be transparent or opaque, can be colored according to the purpose, and can also be evaporated with other layers.

In order to improve the adhesion between the substrate and other layers such as the adhesive layer provided on the substrate, the surface of the substrate may be subjected to convexo-convex treatment such as sandblasting treatment and solvent treatment; and oxidation treatment such as corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, etc. In addition, the surface of the substrate may also be subjected to primer treatment. In addition, the substrate may also have an antistatic coating layer, a layer to prevent the substrate from being attached to other sheets or the substrate from being attached to an adsorption platform when the semiconductor processing sheets are stacked and stored.

The substrate can be manufactured by a known method. For example, a substrate containing a resin can be manufactured by molding a resin composition containing the above-mentioned resin.

[Adhesive layer] The adhesive layer is in a sheet or film form and contains an adhesive. Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins.

In this specification, "adhesive resin" includes both resins having adhesive properties and resins having bonding properties. For example, the aforementioned adhesive resin includes not only resins having adhesive properties themselves, but also resins that exhibit adhesive properties by being used in combination with other components such as additives, and resins that exhibit bonding properties by the presence of triggers such as heat or water.

The adhesive layer may be composed of one layer (single layer) or may be composed of two or more layers. When composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

The thickness of the adhesive layer is not particularly limited, and is preferably 1 μm to 100 μm, more preferably 1 μm to 60 μm, and particularly preferably 1 μm to 30 μm. Here, the so-called "thickness of the adhesive layer" means the thickness of the adhesive layer as a whole. For example, the so-called thickness of an adhesive layer composed of multiple layers means the total thickness of all layers constituting the adhesive layer.

The adhesive layer can be formed using an energy ray curable adhesive or a non-energy ray curable adhesive. That is, the adhesive layer can be either energy ray curable or non-energy ray curable. The energy ray curable adhesive layer can easily adjust the physical properties of the adhesive layer before and after curing.

The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, the adhesive composition is applied to the surface to be formed on the adhesive layer, and dried as needed, thereby forming the adhesive layer on the target site. The ratio of the content of the components that do not vaporize at room temperature in the adhesive composition is usually the same as the ratio of the content of the aforementioned components in the adhesive layer.

The adhesive composition can be applied in the same manner as the adhesive composition described above.

When the adhesive layer is energy ray-curable, the energy ray-curable adhesive composition may include, for example, the following adhesive compositions: an adhesive composition (I-1) containing a non-energy ray-curable adhesive resin (I-1a) (hereinafter, sometimes referred to as "adhesive resin (I-1a)") and an energy ray-curable compound; an adhesive composition (I-2) containing an energy ray-curable adhesive resin (I-2a) having an unsaturated group introduced into the side chain of the aforementioned adhesive resin (I-1a) (hereinafter, sometimes referred to as "adhesive resin (I-2a)"); and an adhesive composition (I-3) containing the aforementioned adhesive resin (I-2a) and an energy ray-curable compound.

When the adhesive layer is non-energy ray-curable, examples of the non-energy ray-curable adhesive composition include an adhesive composition (I-4) containing the aforementioned adhesive resin (I-1a).

The adhesive compositions (I-1) to (I-4) can be produced by the same method as the above-mentioned adhesive composition except that the ingredients are different.

Next, examples of the semiconductor processing sheet according to the present embodiment will be described below for each type of the support sheet, with reference to the drawings.

Fig. 2 is a schematic cross-sectional view of a semiconductor processing sheet according to an embodiment of the present invention. In addition, in the figures after Fig. 2, the same components as those shown in the already described figures are marked with the same symbols as those in the already described figures, and the detailed description of the components is omitted.

The semiconductor processing sheet 101 shown here has a support sheet 10, and a film adhesive 13 is provided on one side (sometimes referred to as "first side" in this specification) 10a of the support sheet 10. The support sheet 10 is composed of only a substrate 11. In other words, the semiconductor processing sheet 101 has a structure in which the film adhesive 13 is layered on one side (sometimes referred to as "first side" in this specification) 11a of the substrate 11. In addition, the semiconductor processing sheet 101 further has a release film 15 on the film adhesive 13.

In the semiconductor processing sheet 101, a film adhesive 13 is deposited on the first surface 11a of the substrate 11, a jig adhesive layer 16 is deposited on a portion of the surface 13a of the film adhesive 13 that is opposite to the side having the substrate 11 (sometimes referred to as the "first surface" in this specification), that is, a region near the periphery, and a peeling film 15 is deposited on the surface of the first surface 13a of the film adhesive 13 where the jig adhesive layer 16 is not deposited and on the surface 16a (upper surface and side surface) of the jig adhesive layer 16 that is not in contact with the film adhesive 13. Here, the first surface 11 a of the substrate 11 is also referred to as the first surface 10 a of the supporting sheet 10 .

The peeling film 15 is the same as the first peeling film 151 or the second peeling film 152 shown in FIG. 1 .

The jig adhesive layer 16 may be, for example, a single-layer structure containing an adhesive component, or a multi-layer structure in which layers containing an adhesive component are laminated on both sides of a sheet serving as a core material.

The semiconductor processing sheet 101 is used by attaching the inner surface of a semiconductor wafer (not shown) to the first surface 13a of the film adhesive 13 with the release film 15 removed, and attaching the upper surface of the surface 16a of the jig adhesive layer 16 to a jig such as a ring frame.

FIG3 is a schematic cross-sectional view of another embodiment of the semiconductor processing sheet of the present invention. The semiconductor processing sheet 102 shown here is the same as the semiconductor processing sheet 101 shown in FIG2 except that it does not have the jig adhesive layer 16. That is, in the semiconductor processing sheet 102, a film adhesive 13 is layered on the first surface 11a of the substrate 11 (the first surface 10a of the support sheet 10), and a peeling film 15 is layered on the entire surface of the first surface 13a of the film adhesive 13. In other words, the semiconductor processing sheet 102 is composed of the substrate 11, the film adhesive 13, and the peeling film 15 layered in sequence in the thickness direction of these layers.

The semiconductor processing sheet 102 shown in FIG. 3 is similar to the semiconductor processing sheet 101 shown in FIG. 2 , in which the peeling film 15 is removed and a portion of the central side of the first surface 13a of the film-like adhesive 13 is attached to the inner surface of a semiconductor wafer (not shown), and then the area near the peripheral portion of the film-like adhesive 13 is attached to a jig such as a ring frame for use.

FIG4 is a schematic cross-sectional view of another embodiment of the semiconductor processing sheet of the present invention. The semiconductor processing sheet 103 shown here is the same as the semiconductor processing sheet 101 shown in FIG2 except that an adhesive layer 12 is further provided between the substrate 11 and the film adhesive 13. The support sheet 10 is a laminate of the substrate 11 and the adhesive layer 12, and the semiconductor processing sheet 103 also has a structure in which a film adhesive 13 is laminated on the first surface 10a of the support sheet 10.

In the semiconductor processing sheet 103, an adhesive layer 12 is laminated on the first surface 11a of the substrate 11, and a film-like adhesive 13 is laminated on the entire surface 12a of the adhesive layer 12 which is opposite to the substrate 11 (sometimes referred to as the "first surface" in this specification), and a first surface 13a of the film-like adhesive 13 is laminated on the first surface 13a of the film-like adhesive 13. A jig adhesive layer 16 is laminated on a portion of a, that is, an area near the periphery, and a peeling film 15 is laminated on the surface of the first surface 13a of the film-like adhesive 13 on which the jig adhesive layer 16 is not laminated, and on the surface 16a (upper surface and side surface) of the jig adhesive layer 16 that is not in contact with the film-like adhesive 13.

The semiconductor processing sheet 103 shown in FIG. 4 is used by attaching the inner surface of a semiconductor wafer (not shown) to the first surface 13a of a film-like adhesive 13 with the release film 15 removed, and then attaching the upper surface of the surface 16a of the jig adhesive layer 16 to a jig such as a ring frame.

FIG5 is a schematic cross-sectional view of another embodiment of the present invention. The semiconductor processing sheet 104 shown here is the same as the semiconductor processing sheet 103 shown in FIG4 except that it does not have a jig adhesive layer 16 and the shape of the film adhesive is different. That is, the semiconductor processing sheet 104 has a substrate 11, an adhesive layer 12 on the substrate 11, and a film adhesive 23 on the adhesive layer 12. The support sheet 10 is a laminate of the substrate 11 and the adhesive layer 12, and the semiconductor processing sheet 104 also has a structure in which a film adhesive 23 is laminated on the first surface 10a of the support sheet 10.

In the semiconductor processing sheet 104, an adhesive layer 12 is deposited on the first surface 11a of the substrate 11, and a film adhesive 23 is deposited on a portion of the first surface 12a of the adhesive layer 12, that is, on the central side. In addition, a peeling film 15 is deposited on the area of the first surface 12a of the adhesive layer 12 where the film adhesive 23 is not deposited, and on the surface 23a of the film adhesive 23 that is opposite to the adhesive layer 12 side (sometimes referred to as the "first surface" in this specification). In FIG. 5 , reference numeral 23 b denotes the other side of the film-like adhesive 23 which is opposite to the first side 23 a (sometimes referred to as the “second side” in this specification).

When the semiconductor processing sheet 104 is viewed from above the peeling film 15 side of the semiconductor processing sheet 104, the surface area of the film adhesive 23 is smaller than that of the adhesive layer 12, and has a circular shape, for example.

The semiconductor processing sheet 104 shown in FIG. 5 is used by attaching the back side of a semiconductor wafer (not shown) to the first surface 23a of the film adhesive 23 with the release film 15 removed, and then attaching the area of the first surface 12a of the adhesive layer 12 where the film adhesive 23 is not deposited to a jig such as a ring frame.

In addition, in the semiconductor processing sheet 104 shown in FIG5, a jig adhesive layer (not shown) may be deposited on the area where the film adhesive 23 is not deposited on the first surface 12a of the adhesive layer 12, similarly to the semiconductor processing sheets shown in FIG2 and FIG4. The semiconductor processing sheet 104 having such a jig adhesive layer is used by attaching the upper surface of the jig adhesive layer to a jig such as a ring frame, similarly to the semiconductor processing sheets shown in FIG2 and FIG4.

In this way, the semiconductor processing sheet can be provided with a jig adhesive layer regardless of the form of the support sheet and the film-like adhesive. However, as a semiconductor processing sheet provided with a jig adhesive layer, a semiconductor processing sheet provided with a jig adhesive layer on a film-like adhesive is generally preferred as shown in FIG. 2 and FIG. 4 .

The semiconductor processing sheet of this embodiment is not limited to the semiconductor processing sheet shown in Figures 2 to 5. Within the scope of not damaging the effect of the present invention, part of the structure of the semiconductor processing sheet shown in Figures 2 to 5 can be changed or deleted, or other structures can be added to the semiconductor processing sheet described above.

For example, the semiconductor processing sheet shown in FIGS. 2 to 5 may also be provided with layers other than the substrate, adhesive layer, film adhesive, and peeling film at any position. In addition, in the semiconductor processing sheet, a partial distance may be generated between the peeling film and the layer directly contacting the peeling film. In addition, in the semiconductor processing sheet, the size or shape of each layer may be arbitrarily adjusted according to the purpose.

◇Usage of film adhesive and semiconductor processing sheet The film adhesive and semiconductor processing sheet of this embodiment can be used to manufacture semiconductor packages and semiconductor devices by manufacturing semiconductor chips with film adhesive.

After the film-like adhesive without a support sheet is attached to the inner surface of the semiconductor wafer, the peeling film is removed as needed, and a dicing sheet is attached to the exposed surface of the film-like adhesive (in other words, the surface opposite to the side attached to the semiconductor wafer. In this manual, it is sometimes referred to as the "second surface"). The dicing sheet, film-like adhesive and semiconductor wafer obtained in this way are sequentially stacked in the thickness direction to form a laminated structure, which is then supplied to a known dicing step. In addition, the laminated structure of the dicing sheet and the film-like adhesive can be regarded as a wafer bonding chip.

In this specification, a laminated structure formed by laminating the wafer or the semiconductor processing sheet and the semiconductor wafer in this manner is sometimes referred to as a "first laminated structure".

By performing the dicing step, the semiconductor wafer is divided into a plurality of semiconductor chips, and the film adhesive is also cut along the periphery of the semiconductor chip, thereby obtaining a plurality of semiconductor chips with the cut film adhesive inside (i.e., semiconductor chips with film adhesive). These plurality of semiconductor chips with film adhesive are fixed in an arranged state on the dicing sheet.

In this specification, a multilayer structure in which a plurality of semiconductor chips with film-like adhesives are fixed in an aligned state on a dicing sheet or the aforementioned support sheet is sometimes referred to as a "second multilayer structure".

On the other hand, the aforementioned semiconductor processing sheet already has a structure as a wafer for wafer cutting. Therefore, at the stage where the semiconductor processing sheet is attached to the inner surface of the semiconductor wafer, a laminated structure (i.e., the aforementioned first laminated structure) is obtained in which the semiconductor processing sheet (cutting sheet, film adhesive) and the semiconductor wafer are sequentially laminated in the thickness direction of these layers. Subsequently, as described above, a dicing step is performed using the same method as in the case of using a film adhesive without a support sheet, thereby obtaining a second laminated structure including a plurality of semiconductor chips with film adhesives.

As a method for dicing a semiconductor wafer, for example, a method using a blade (that is, blade dicing) can be cited, but the present invention is not limited to this, and all known methods for singulating a semiconductor wafer can be applied.

When using either a film adhesive or a semiconductor processing sheet, the film adhesive of this embodiment is provided on the back surface of the semiconductor wafer in the dicing step, so that chip splashing is suppressed.

When using either a film adhesive or a semiconductor processing sheet, the semiconductor chip with the film adhesive is subsequently pulled away from the cutting sheet or the supporting sheet and picked up, and bonded to the circuit forming surface of the substrate by the film adhesive. After bonding, a semiconductor package and a semiconductor device are manufactured using the same method as the previous method. For example, if necessary, one or more semiconductor chips are stacked on the semiconductor chip after bonding, and then wire bonding is performed. Then, the film adhesive is thermally cured, and the obtained laminated structure is sealed as a whole by a resin. By going through these steps, a semiconductor package is manufactured. And the target semiconductor device is manufactured using the semiconductor package.

The semiconductor package obtained in this way has higher reliability by using the film adhesive of this embodiment. For example, in the semiconductor package before and after assembly, peeling is suppressed in the film adhesive-related joints such as the joint between the substrate and the semiconductor chip and the joint between the semiconductor chips. [Example]

The present invention is described in more detail below by using specific embodiments. However, the present invention is not limited to the embodiments shown below.

[Monomer] In the present embodiment and comparative example, the formal names of the abbreviated monomers are as follows. BA: n-butyl acrylate MA: methyl acrylate EA: ethyl acrylate HEA: 2-hydroxyethyl acrylate AN: acrylonitrile GMA: glycidyl methacrylate

[Raw materials for producing adhesive composition] In this embodiment and comparative example, the raw materials used for producing adhesive composition are shown below.

[Polymer component (a)] (a)-1: Acrylic resin (weight average molecular weight 700,000, glass transition temperature 14°C) obtained by copolymerizing BA (40 parts by mass), EA (25 parts by mass), AN (30 parts by mass) and GMA (5 parts by mass). (a)-2: Acrylic resin (weight average molecular weight 800,000, glass transition temperature -28°C) obtained by copolymerizing BA (55 parts by mass), MA (10 parts by mass), GMA (20 parts by mass) and HEA (15 parts by mass). (a)-3: Thermoplastic resin, polyester ("Vylon" manufactured by Toyobo Co., Ltd.) 220", number average molecular weight 3000, glass transition temperature 53℃) [Epoxy resin (b1)] (b1)-1: Bisphenol A type epoxy resin ("JER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184g/eq to 194g/eq) (b1)-2: Cresol novolac type epoxy resin ("EOCN-103S" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 209g/eq to 219g/eq) (b1)-3: Phenol novolac type epoxy resin ("EOCN-104S" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 213g/eq to 223g/eq) (b1)-4: Liquid bisphenol A type epoxy resin =Mixture of epoxy resin and acrylic rubber particles ("BPA328" manufactured by Nippon Catalyst Co., Ltd., epoxy equivalent 235g/eq) (b1)-5: Polyfunctional aromatic type (terphenyl type) epoxy resin ("EPPN-502H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 167g/eq, softening point 54℃, weight average molecular weight 1200) (b1)-6: Bisphenol A type epoxy resin ("JER1055" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent 800g/eq to 900g/eq) [Thermosetting agent (b2)] (b2)-1: o-cresol type phenolic varnish resin ("Phenolite =KA-1160", hydroxyl equivalent 117g/eq, softening point 80℃, resin represented by general formula (1) with n being 6 to 7) (b2)-2: Novolac type phenolic resin ("BRG556" manufactured by Showa Denko) (b2)-3: Thermally active latent epoxy resin hardener: dicyandiamide ("EH-3636AS" manufactured by ADEKA, active hydrogen 21g/eq) [Hardening accelerator (c)] (c)-1: 2-phenyl-4,5-dihydroxymethylimidazole ("Curezol 2PHZ-PW”) [Filling material (d)] (d)-1: Spherical silica modified with epoxy groups (“ADMANANO YA050C-MKK” manufactured by Admatechs, average particle size 50nm) (d)-2: Silica filler (“SC2050MA” manufactured by Admatechs, silica filler with epoxy-based compound surface modification, average particle size 500nm) [Coupling agent (e)] (e)-1: Oligomer-type silane coupling agent with epoxy, methyl and methoxy groups (Shin-Etsu ="X-41-1056" manufactured by Silicones, epoxy equivalent 280g/eq) (e)-2: Silicate compound formed by adding 3-glycidyloxypropyltrimethoxysilane ("MKC Silicate MSEP2" manufactured by Mitsubishi Chemical Corporation) (e)-3: Trimethoxy[3-(phenylamino)propyl]silane ("SZ6083" manufactured by DOW TORAY, silane coupling agent) [Crosslinking agent (f)] (f)-1: TDI-based isocyanate crosslinking agent (Coronate L manufactured by Tosoh Corporation, solid content concentration 75% by mass) [Energy ray curing resin (g)] (g)-1: Tricyclodecane dihydroxymethyl diacrylate ("KAYARAD" manufactured by Nippon Kayaku Co., Ltd.) R-684", UV curable resin, molecular weight 304) (g)-2: A mixture of dipentaerythritol hexaacrylate (6-functional UV curable compound, molecular weight 578) and dipentaerythritol pentaacrylate (5-functional UV curable compound, molecular weight 525) ("KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd.) [Photopolymerization initiator (h)] (h)-1: 1-Hydroxycyclohexyl phenyl ketone ("IRGACURE (registered trademark) 184" manufactured by BASF) [Other thermal curing agents (b20)] (b20)-1: An o-cresol-type phenolic varnish resin having a softening point of 160°C manufactured by the method described below. The number of repetitions corresponding to n in the general formula (1): 18 to 24

[Production Example 1] [Production of other heat curing agent (b20)-1] In a separable flask equipped with a thermometer, a stirrer and a reflux cooler, o-cresol (100 parts by mass), paraformaldehyde (33.0 parts by mass) with a concentration of 92% by mass, and oxalic acid (1.0 parts by mass) were added, and the obtained mixture was reacted for 4 hours while being refluxed. Then, methyl isobutyl ketone (50.0 parts by mass) was added to the obtained reaction solution, and the reaction was carried out at 120°C for 5 hours. Then, the obtained reaction solution was heated to 180°C and depressurized to remove methyl isobutyl ketone from the reaction solution. Next, the resin melted at 180°C was extracted and cooled to obtain a solid o-cresol type novolac resin (other heat curing agent (b20)-1).

[Example 1] [Manufacturing of film-like adhesive] [Manufacturing of adhesive composition] Polymer component (a)-1 (10 parts by mass), epoxy resin (b1)-1 (25.8 parts by mass), epoxy resin (b1)-2 (23 parts by mass), thermosetting agent (b2)-1 (25 parts by mass), curing accelerator (c)-1 (0.2 parts by mass), filler (d)-1 (15 parts by mass), and coupling agent (e)-1 (1 part by mass) are dissolved or dispersed in methyl ethyl ketone, and stirred at 23°C to obtain an adhesive composition having a total concentration of all the above components of 50% by mass. In addition, the amounts of the components other than methyl ethyl ketone shown here are all the amounts of the target product without the solvent component.

[Manufacturing of film-like adhesive] A release film ("SP-PET381031" manufactured by Lintec Corporation, 38μm thick) made of polyethylene terephthalate (PET) film with one side subjected to release treatment by polysilicone treatment was used, and the adhesive composition obtained above was applied to the release-treated surface of the release film, and then heated and dried at 100°C for 1 minute to form a film-like adhesive with a thickness of 20μm.

[Manufacturing of semiconductor processing sheet] A polyethylene film (manufactured by GUNZE, thickness 80 μm) is laminated as a substrate to the surface of the film-like adhesive obtained above that is opposite to the side having the release film (in other words, the exposed surface), thereby obtaining a semiconductor processing sheet composed of the substrate, the film-like adhesive and the release film being layered in this order in the thickness direction of these layers.

[Evaluation of film adhesive] [Measurement of storage modulus G'] After laminating the film adhesive obtained above with a thickness of 20μm just after production and before heat curing, the laminate was punched out to obtain a φ10mm×1mm test piece. Using a viscoelasticity measuring device (ARES manufactured by Rheometric Scientific), the storage modulus G' from 0℃ to 100℃ was measured under the measurement conditions of frequency: 11Hz and heating rate: 10℃/min. Among them, the value of storage modulus G' (without elapsed time) [Pa] at 80℃ was obtained. In addition, the film-like adhesive just after production and before heat curing was stored in an air atmosphere at 40°C for 7 days (with time), and the storage modulus G' was measured in the same manner as the storage modulus G' (without time) described above, to obtain the value of the storage modulus G' (with time) [Pa] at 80°C.

[Air Residual Rate Test] [Manufacturing of Chips with Film-like Adhesive] The release film is removed from the semiconductor processing sheet just manufactured as described above. The semiconductor processing sheet is immediately attached to a quartz glass wafer (150 mm in diameter, 100 μm in thickness) via the film-like adhesive using a tape bonding device ("Adwill RAD2500" manufactured by Lintec) at room temperature. By the above steps, a semiconductor processing sheet without an age history is used to obtain a first laminated structure (sometimes referred to as "first laminated structure (1-1)" in which a substrate, a film-like adhesive, and a quartz glass wafer are laminated in sequence in the thickness direction of these layers) using the semiconductor processing sheet without an age history.

Next, the exposed surface of the film adhesive in the first multilayer structure (1-1) that is not attached to the periphery of the glass wafer is fixed to a ring frame for cutting. Next, a cutting device ("DFD6362" manufactured by DISCO) is used to cut the glass wafer and the film adhesive is cut to obtain a glass chip of 10 mm x 10 mm in size. The dicing at this time is performed in the following manner: the moving speed of the dicing blade is set to 5mm/sec, the rotation speed of the dicing blade is set to 50000rpm, and the dicing blade is used to cut into the semiconductor processing sheet until the film adhesive is 40μm deep from the glass wafer attachment surface (that is, until the entire area in the thickness direction of the film adhesive and the area where the substrate is 20μm deep from the layer surface of the film adhesive side). As a dicing blade, "R07-SDC400-BB300-100 54×0.23A2×40" manufactured by DISCO is used. Through the above steps, a semiconductor processing sheet having a film-like adhesive before heat curing without a time history is used to obtain a second multilayer structure (sometimes referred to as "second multilayer structure (1-1)" in which a plurality of chips having a film-like adhesive after cutting on the back side (in other words, a plurality of chips with a film-like adhesive) are fixed on a substrate in an arranged state by the film-like adhesive.

[Chip bonding with film-like adhesive to substrate] Preparation of substrate for air residue test (Cu electrode formed on glass substrate of 30mm×30mm×0.5mm). Figure 6 shows a schematic diagram of the above substrate for air residue test. On the substrate 130, comb-shaped electrodes 32 and 33 with a wiring pattern shown in Figure 6 are formed on a glass substrate 30 with a line/space (L/S) of 100μm/100μm and an electrode thickness of 10μm. In addition, the size and number of the wiring pattern shown in Figure 6 are different from the actual ones.

The chip with film-like adhesive in the second multilayer structure (1-1) obtained above was picked up from the substrate using a manual die bonding device ("EDB65" manufactured by CAMMAX Precima). Then, the film-like adhesive in the picked-up chip with film-like adhesive was pressed onto the bonding position (position B in the figure) 10mm×10mm shown in Figure 6 on the circuit forming surface of the aforementioned substrate, thereby bonding the chip with film-like adhesive to the aforementioned substrate. The die bonding at this time was performed in the following manner: a force of 1.96N (200gf) was applied to the silicon chip with film-like adhesive heated to 80°C in a direction orthogonal to the contact surface between the aforementioned silicon chip and the aforementioned substrate for 1 second. By the above steps, a semiconductor processing sheet having a film-like adhesive before heat curing without aging is obtained to obtain an air retention rate test substrate (sometimes referred to as "air retention rate test substrate (without aging)" in this specification).

The semiconductor processing sheet just manufactured as above is stored in an air atmosphere at 40°C for 7 days. Then, a substrate is obtained by the same method as the above-mentioned air residue test substrate (without aging), except that the semiconductor processing sheet after storage, i.e., after aging, is used instead of the above-mentioned semiconductor processing sheet just manufactured. Through the above steps, an air residue test substrate (sometimes referred to as "air residue test substrate (with aging)" in this manual) is obtained using a semiconductor processing sheet having a film adhesive before heat curing with an aging history.

Then, using a digital microscope (VHX-1000 manufactured by Keyence Corporation), the above-produced substrate for air retention rate test (without time) and the substrate for air retention rate test (with time) were observed coaxially from the glass wafer side of the substrate. Since the line (L) portion of the substrate is formed in a convex shape in the direction of the film adhesive corresponding to the height of the wiring, it is easy to be in close contact with the film adhesive, and it is observed that the entire area of the L portion is in close contact with the film adhesive. In contrast, the spacing (S) portion is formed in a concave shape in the direction of the film adhesive corresponding to the height of the wiring, so it is not easy to be in close contact with the film adhesive, and sometimes it is observed that there is air in a part between the glass substrate and the film adhesive (air residue). In the obtained image, the air-residual part is confirmed in white, and the non-air-residual part is confirmed in gray, which can be easily distinguished in the form of color difference. After observation in the above manner, the image obtained above is binarized by the following method using image analysis software ("ImagePro" manufactured by NIPPON ROPER). That is, for the above image, a 256-pixel histogram is automatically calculated on the above software, and the processing is performed using the median value of the histogram. From the air residue rate measurement position shown in Figure 6 (the position of M in the figure, i.e. the central part of the joint position B), 5 areas with a spacing of 1.1mm×5.0mm are captured. The areas corresponding to the air residue in these areas are set to white and classified as air residue areas, and the remaining areas are set to black and classified as non-air residue areas, and the above-mentioned image is corrected. In the obtained corrected image, a virtual color contour is allocated, and the relative area and ratio are calculated. Through the above steps, a binary image is obtained, and the area value A of the air residual area in the area of the spacing part and the area value B of the non-air residual area in the area of the spacing part are obtained, and the air residual rate (area%) in the spacing part 100% area is calculated = A/(A+B)×100. The results are shown in Table 1.

[Evaluation of the reliability of semiconductor packages] [Manufacturing of semiconductor chips with film-like adhesives] The peeling film was removed from the semiconductor processing sheet just manufactured as described above. A silicon wafer (diameter 200 mm, thickness 75 μm) whose back side was ground by dry polishing was used, and the semiconductor processing sheet was immediately attached to the back side (ground side) of the silicon wafer using a tape bonding device ("Adwill RAD2500" manufactured by Lintec) at room temperature. Through the above steps, using a semiconductor processing sheet without a time history, a first multilayer structure (sometimes referred to as "first multilayer structure (1-2)" in this specification) is obtained, in which a substrate, a film adhesive, and a silicon wafer are sequentially stacked in the thickness direction of these layers.

Next, the exposed surface of the film adhesive in the first multilayer structure (1-2) that is not attached to the periphery of the silicon wafer is fixed to a ring frame for wafer dicing. Next, dicing is performed using a dicing device ("DFD6361" manufactured by DISCO Corporation) to separate the silicon wafer and cut off the film adhesive, thereby obtaining a silicon chip of 8 mm × 8 mm in size. The dicing at this time is performed in the following manner: the moving speed of the dicing blade is set to 30mm/sec, the rotation speed of the dicing blade is set to 30000rpm, and the dicing blade is used to cut into the semiconductor processing sheet until the film adhesive is 40μm deep from the silicon wafer attachment surface (that is, until the entire area in the thickness direction of the film adhesive and the area where the substrate is 20μm deep from the surface of the film adhesive side). As a dicing blade, "Z05-SD2000-D1-90 CC" manufactured by DISCO is used. Through the above steps, using a semiconductor processing sheet without a time history, a plurality of silicon chips having a film-like adhesive on the back side after cutting (in other words, a plurality of silicon chips with a film-like adhesive) are obtained, and the second multilayer structure (sometimes referred to as "the second multilayer structure (1-2)" in this specification) is fixed on the substrate in an arranged state by the film-like adhesive.

[Die bonding of semiconductor chip with film adhesive to substrate] As a substrate, the following substrate ("SM15-031-10A" manufactured by Shiima Electronics, size: 157.0mm×70.0mm×0.2mm) was prepared: a circuit pattern was formed on the copper foil (thickness 15μm) of a copper foil-clad laminate ("CCL-HL830" manufactured by Mitsubishi Gas Chemical Co., Ltd.), and a layer of solder resist ("PSR-4000 AUS308" manufactured by Solar Ink Co., Ltd.) was formed on the circuit pattern.

The pick-up-and-bonding device ("BESTEM D-02" manufactured by Canon Machinery) is used to pick up the silicon wafer with film-like adhesive in the second multilayer structure (1-2) obtained above from the substrate. Then, the film-like adhesive in the picked-up silicon wafer with film-like adhesive is pressed onto the aforementioned substrate, thereby bonding the silicon wafer with film-like adhesive to the aforementioned substrate. At this time, bonding is performed by applying a force of 2.45N (250gf) for 0.5 seconds to the silicon wafer with film-like adhesive heated to 120°C in a direction orthogonal to the contact surface between the aforementioned silicon wafer and the aforementioned substrate. Through the above steps, a substrate with a semiconductor wafer with film-like adhesive bonded is obtained.

[Manufacturing of semiconductor package (1)] The die-bonded substrate obtained above was heated at 160°C for 1 hour to thermally cure the film adhesive on the substrate. Next, a sealing resin ("KE-1100AS3" manufactured by KYOCERA Chemical) was placed on the die-bonded and thermally cured substrate using a sealing device ("MPC-06M TriAl Press" manufactured by APIC YAMADA), and the sealing resin was heated to 175°C. A pressure of 7 MPa was applied to the sealing resin in this state for 2 minutes to form a layer (sealing layer) composed of the sealing resin with a thickness of 400 μm. Next, the sealing resin formed with the sealing layer was heated at 175°C for 5 hours to thermally cure it, thereby obtaining a sealed substrate.

Next, a dicing tape ("Adwill D-510T" manufactured by Lintec) is attached to the sealing substrate, and a dicing device ("DFD6361" manufactured by DISCO) is used to cut the sealing substrate to obtain a semiconductor package of 15mm×15mm in size. The cutting is performed in the following manner: the moving speed of the dicing blade is set to 50mm/sec, the rotation speed of the dicing blade is set to 30000rpm, and the dicing blade is used to cut into the dicing tape until the dicing tape is 40μm deep from the sealing substrate attachment surface. As a dicing blade, "ZHDG-SD400-D1-60 56×0.17A3×40-L-S3" manufactured by DISCO is used. Through the above steps, the target semiconductor package (sometimes referred to as "semiconductor package (1)" in this specification) is obtained using a semiconductor processing sheet without an age history. Here, 25 semiconductor packages (1) are obtained using the above method.

[Manufacturing of semiconductor package (2)] The semiconductor processing sheet just manufactured was stored in an air atmosphere at 40°C for 7 days. Then, a semiconductor package was obtained by the same method as the semiconductor package (1) except that the semiconductor processing sheet just manufactured was replaced with the semiconductor processing sheet after storage, i.e. after aging. Through the above steps, the target semiconductor package (sometimes referred to as "semiconductor package (2)" in this specification) was obtained using the semiconductor processing sheet after aging. Here, 25 semiconductor packages (2) were obtained by the above method.

[Evaluation of the reliability of semiconductor packages] The 25 semiconductor packages (1) obtained above were stored in an environment of 85°C and 60% relative humidity for 168 hours to absorb moisture. Then, the semiconductor packages (1) after moisture absorption were immediately preheated at 160°C and subjected to IR (Infrared Radiation) reflow three times, with the maximum temperature set to 260°C and heated for 1 minute. The IR reflow was performed using a tabletop reflow furnace ("STR-2010N2M" manufactured by Senju Metal Industries).

Next, the semiconductor package after IR reflow was analyzed using a scanning ultrasonic flaw detector ("D-9600" manufactured by Sonoscan). In addition, the semiconductor package after IR reflow was cut using a cross-section grinder ("Refine Polisher HV" manufactured by Refine Tec) to form a cross section, which was observed using a digital microscope ("VHX-1000" manufactured by Keyence). In addition, in at least one of the joints between the substrate and the silicon wafer and the joints between the silicon wafers, if peeling of 0.5 mm or more was confirmed, it was judged as "peeling was present", and if it was not confirmed, it was judged as "no peeling". Furthermore, based on the judgment result, the reliability of the semiconductor package (1) is evaluated according to the following criteria. (Evaluation Criteria) A: The number of semiconductor packages judged as "peeling" is 3 or less. B: The number of semiconductor packages judged as "peeling" is 4 or more.

Furthermore, the reliability of semiconductor package (2) was evaluated using the same method as in the case of semiconductor package (1) described above. The evaluation results of these semiconductor packages (1) and (2) are shown in Table 1 together with the number of semiconductor packages judged to have "peeling" (indicated in parentheses in the corresponding column of Table 1).

[Manufacturing and evaluation of film-like adhesive] [Comparative Examples 1 to 3] The types and contents of the components contained in the adhesive composition are as shown in Table 1. One or both of the types and amounts of the components prepared when manufacturing the adhesive composition are changed. Except for this, the same method as in Example 1 is used to manufacture film-like adhesives and semiconductor processing sheets, and the film-like adhesives are evaluated. The results are shown in Table 1.

In addition, when "-" is written in the column of the contained component in Table 1, it means that the adhesive composition does not contain the component.

[Table 1] Embodiment 1 Comparison Example 1 Comparison Example 2 Comparison Example 3 Ingredients in adhesive composition (by weight) Polymer component (a) (a)-1 10 - - 10 (a)-2 - 10 18 - (a)-3 - 20 - - Epoxy resin (b1) (b1)-1 25.8 - - 25.8 (b1)-2 23.0 - - 23.0 (b1)-3 - - 9.0 - (b1)-4 - 20.0 26.0 - (b1)-5 - 20.0 - - (b1)-6 - - 34.0 - Heat curing agent (b2) (b2)-1 25 - - - (b2)-2 - 20 - - (b2)-3 - - 1 - Heat curing agent (b20) (b20)-1 - - - 25 Hardening accelerator (c) (c)-1 0.2 0.3 1.0 0.2 Filling material (d) (d)-1 15 - - 15 (d)-2 - 10 - - Coupling agent (e) (e)-1 1 - - 1 (e)-2 - 0.5 0.5 - (e)-3 - 0.3 - - Crosslinking agent (f) (f)-1 - - 0.2 - Energy ray curing resin (g) (g)-1 - 5 - - (g)-2 - - 10 - Photopolymerization initiator(h) (h)-1 - 0.15 0.30 - Evaluation results G'80℃(no elapsed time)[Pa] 1.8×10 ³ 5.1×10 ³ 3.7×10 ⁴ 6.7×10 ⁴ G'80℃(with elapsed time)[Pa] 2.3×10 ³ 6.2×10 ⁴ 4.0×10 ⁴ 7.1×10 ⁴ Air Residual Rate (No Time) [Area %] 13 17 29 33 Air Residual Rate (Over Time) [Area %] 15 34 30 36 Reliability of semiconductor packages (number of “peeled off” components) Semiconductor package (1) (no time) A(0) A(0) B(25) B(21) Semiconductor Package (2) (Time) A(0) B(25) B(25) B(23)

It is clear from the above results that if the storage elastic modulus G' of the film adhesive at 80°C is below 3×10 ⁴ Pa, the air retention rate of the film adhesive is low, and it is not easy to produce peeling in the manufactured semiconductor package, and the reliability is high. Even after the film adhesive of Example 1 is stored at 40°C for 7 days (with time), the storage elastic modulus G' is suppressed to below 3×10 ⁴ Pa, and the storage stability is significantly excellent. [Industrial Applicability]

The present invention can be used to manufacture semiconductor devices.

10: Support sheet 10a: 1st side of support sheet 11: Base material 11a: 1st side of base material 12: Adhesive layer 12a: 1st side of adhesive layer 13,23: Film adhesive 13a,23a: 1st side of film adhesive 13b,23b: 2nd side of film adhesive 15: Peeling film 16: For jig Adhesive layer 16a: Upper and side surfaces of the adhesive layer for jig 30: Glass substrate 32,33: Electrodes 101,102,103,104: Semiconductor processing sheet 130: Substrate 151: First peeling film 152: Second peeling film B: Bonding position L: Line S: Spacing M: Air residue rate measurement position

[FIG. 1] is a schematic cross-sectional view of a film adhesive of one embodiment of the present invention. [FIG. 2] is a schematic cross-sectional view of a semiconductor processing sheet of one embodiment of the present invention. [FIG. 3] is a schematic cross-sectional view of another semiconductor processing sheet of the present invention. [FIG. 4] is a schematic cross-sectional view of another semiconductor processing sheet of the present invention. [FIG. 5] is a schematic cross-sectional view of another semiconductor processing sheet of the present invention. [FIG. 6] is a top view of a substrate used for an air residual rate test in an embodiment.

10: Support sheet

10a: Surface 1 of the support sheet

11: Base material

11a: Surface 1 of the substrate

13: Film adhesive

13a: The first side of the film adhesive

13b: The second side of the film adhesive

15: Peel off membrane

16: Adhesive layer for jigs

16a: The upper surface and side surface of the adhesive layer for the jig

101: Sheets for semiconductor processing

Claims (4)

A film adhesive is thermosetting; before being stored at 40°C for 7 days and before being thermoset, and after being stored at 40°C for 7 days and before being thermoset, the film adhesive satisfies the following requirements 1) and 2): 1) The storage elastic modulus G' of the film adhesive at 80°C is 3×10 ⁴ Pa or less; 2) on the copper wiring side of a glass substrate having a copper wiring with a line/space (L/S) of 100 μm/100 μm and a thickness of 10 μm, in an area of 1.1 mm×5 mm in the central part of a portion where a 10 mm×10 mm×20 μm film-like adhesive is pressed at 80°C with a load of 1.96 N for 1 second, the air retention rate in 100% by area of the spacing portion is 20% by area or less; the film-like adhesive contains a polymer component (a), an epoxy resin (b1), and a thermosetting agent (b2); the polymer component (a) is an acrylic resin; the thermosetting agent (b2) is a resin represented by the following general formula (1) having a softening point of 60°C to 130°C;

Furthermore, in the general formula (1), n is an integer greater than or equal to 1. The film adhesive as described in claim 1, wherein the thickness of the film adhesive is 5μm to 50μm. A semiconductor processing sheet having a support sheet, and a film adhesive as described in claim 1 or 2 is provided on one surface of the support sheet. The semiconductor processing sheet as described in claim 3, wherein the supporting sheet comprises a substrate and an adhesive layer disposed on one surface of the substrate; the adhesive layer is disposed between the substrate and the film-like adhesive.

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